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  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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  • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
  • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
  • C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine groups
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
  • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
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  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
  • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
  • C08J9/141—Hydrocarbons
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  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
  • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
  • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
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  • C08G2101/00—Manufacture of cellular products
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  • C08G2110/00—Foam properties
  • C08G2110/0025—Foam properties rigid
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  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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  • C08J2205/00—Foams characterised by their properties
  • C08J2205/10—Rigid foams
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  • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2375/04—Polyurethanes
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  • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
  • C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
  • C08J2483/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences

Definitions

• the present invention is in the field of rigid polyurethane foams. More particularly, it relates to the production of rigid polyurethane foams using specific siloxane compounds, and additionally to the use of the foams which have been produced therewith.
• Polyurethane (PU) in the context of the present invention is especially understood to mean a product obtainable by reaction of polyisocyanates and polyols, or compounds having isocyanate-reactive groups. Further functional groups in addition to the polyurethane can also be formed in the reaction, examples being uretdiones, carbodiimides, isocyanurates, allophanates, biurets, ureas and/or uretonimines. Therefore, PU is understood in the context of the present invention to mean both polyurethane and polyisocyanurate, polyureas, and polyisocyanate reaction products containing uretdione, carbodiimide, allophanate, biuret and uretonimine groups.
• polyurethane foam is especially understood to mean foam which is obtained as reaction product based on polyisocyanates and polyols or compounds having isocyanate-reactive groups.
• the reaction to give what is named a polyurethane can form further functional groups as well, examples being allophanates, biurets, ureas, carbodiimides, uretdiones, isocyanurates or uretonimines.
• Rigid polyurethane and polyisocyanurate foams are produced using cell-stabilizing additives to ensure a fine-celled, uniform and low-defect foam structure and hence to exert an essentially positive influence on the performance characteristics, particularly the thermal insulation performance, of the rigid foam.
• Surfactants based on polyether-modified siloxanes are particularly effective and therefore represent the preferred type of foam stabilizers.
• PES polyethersiloxane foam stabilizers
• EP 0 570 174 B1 describes polyethersiloxanes suitable for the production of rigid polyurethane foams using organic blowing agents, particularly chlorofluorocarbons such as CFC-11.
• EP 0 533 202 A1 describes polyethersiloxanes that bear SiC-bonded polyalkylene oxide radicals and are suitable as blowing agent in the case of use of hydrochlorofluorocarbons, for example HCFC-123.
• EP 0 877 045 B1 describes analogous structures for this production process which differ from the former foam stabilizers in that they have a comparatively higher molecular weight and have a combination of two polyether substituents on the siloxane chain.
• EP1544235 describes typical polyether-modified siloxanes for rigid PU foam applications. Siloxanes having 60 to 130 silicon atoms and different polyether substituents R, the mixed molar mass of which is 450 to 1000 g/mol and the ethylene oxide content of which is 70 to 100 mol %, are used here.
• CN103055759 describes polyether-modified siloxanes that bring about improved cell opening. At least 18 silicon units are present in the siloxane, and various types of side chains are used for modification.
• EP 1873209 describes polyether-modified siloxanes for production of rigid PU foams having improved fire properties.
• the polyether side chains consist to an extent of at least 90% of ethylene oxide units.
• EP 2465891 A1 describes polyether-modified siloxanes in which some of the polyether side chains bear OH groups.
• the siloxanes here contain at least 10 silicon atoms.
• EP 2465892 A1 describes polyether-modified siloxanes in which the polyether side chains bear mainly secondary OH end groups.
• the siloxanes contain at least 10 silicon atoms.
• Siloxanes that do not contain any polyether modification are known mainly as additives in flexible polyurethane foam, especially moulded foam.
• EP1095968A1 which describes polydimethylsiloxanes for flexible foam having preferably 7-9 silicon atoms
• DE4444898 C1 which describes the production of cold-cure foams with alkylaryl-modified siloxanes containing 5-16 silicon atoms.
• DE 3215317 C1 describes the production of cold-cure foams with siloxanes that have been modified with allyl glycidyl ether and then reacted with amines. Here too, not more than 10 silicon atoms are present in siloxanes.
• EP0258600A2 describes cold-cure foams with chloropropyl-modified siloxanes having 3-20 silicon units and 1-8 side chain modifications.
• EP2368927A1 describes the production of rigid PU foam using CO 2 as blowing agent and two different polyol types, one based on phenolic resins, prepared from novolaks and alkylene oxides, and one based on aromatic amine polyols, prepared by alkoxylation of aromatic amines.
• polydimethylsiloxanes such as hexamethyldisiloxane in particular.
• the problem addressed by the present invention was that of providing rigid polyurethane or polyisocyanurate foams that have particularly advantageous use properties, such as, in particular, low thermal conductivity and/or good surface quality.
• inventive polyalkylsiloxanes in interplay with polyether-modified siloxanes, enables corresponding improvements.
• the polyalkylsiloxanes according to the invention do not contain any polyether modification.
• the inventive polyalkylsiloxanes contain fewer than 20, preferably fewer than 15 and more preferably fewer than 11 silicon atoms.
• inventive polyalkylsiloxanes are used in combination with polyether-modified siloxanes in a mass ratio of 1:5 to 1:200.
• Polyether-modified siloxanes used may be the known structures according to the prior art that are suitable for production of rigid PU foams. These are known to those skilled in the art.
• inventive polyalkylsiloxanes and polyether-modified siloxanes may be added separately or as a mixture to the compound to be foamed.
• inventive polyalkylsiloxanes When the inventive polyalkylsiloxanes are added separately, they are preferably added in a carrier medium (solvent).
• carrier medium examples include glycols, alkoxylates or oils of synthetic and/or natural origin.
• inventive polyalkylsiloxanes conform to the formula (1):
• R 11 , R 12 , R 13 , R 14 , R 15 , R 16 identical or different hydrocarbon radicals having 1 to 12 carbon atoms, where the hydrocarbon radicals are optionally substituted by heteroatoms, excluding oxygen, or H, preferably identical or different hydrocarbon radicals having 1-8 carbon atoms, where the hydrocarbon radicals are optionally substituted by heteroatoms, excluding oxygen, or H, especially preferably the radicals: phenyl-, CH 3 —, CH 3 CH 2 —, CH 2 CH— ClCH 2 CH 2 CH 2 — and H—.
• a 2-6
• b 0-8
• c+d>0.5; especially preferably, c+d> 1.
• R 16 is different from R 11 , R 12 , R 13 , R 14 and R 15 .
• R 11 , R 12 , R 13 are different, and so the M unit in the siloxane bears two or three different radicals.
• Preferred polyalkylsiloxanes conform to the formula 2:
• Preferred polyalkylsiloxanes of the formula 2 conform to the formula 3 or 4:
• Preferred polyalkylsiloxanes are as follows:
• the polyether-modified siloxanes are described more specifically hereinafter.
• Preferred polyether-modified siloxanes can be described by the following formula:
• n is independently 0 to 500, preferably 1 to 300 and especially 2 to 150
• m is independently 0 to 60, preferably 1 to 50 and especially 1 to 30
• p is independently 0 to 10, preferably 0 or >0 to 5
• k is independently 0 to 10, preferably 0 or >0 to 5, with the proviso that, for each molecule of the formula (1), the average number ⁇ k of T units and the average number ⁇ p of Q units per molecule is not greater than 50 in either case, the average number ⁇ n of D units per molecule is not greater than 2000 and the average number ⁇ m of the siloxy units bearing R 1 per molecule is not greater than 100,
• z can be 0 or 1
• Particularly preferred polyether-modified siloxanes conform to the formula 5
• At least one R 2 radical is the same as R 1 .
• polyether-modified siloxanes of the formula 5 are used, where the molar proportion of oxyethylene units amounts to at least 70% of the oxyalkylene units, i.e. x/(x+y)>0.7. It may also be advantageous when the polyoxyalkylene chain bears a hydrogen or a methyl group at its end and, at the same time, the molar proportion of oxyethylene units accounts for not more than 70% of the oxyalkylene units, i.e. x/(x+y) ⁇ 0.7, and R 5 is a hydrogen or methyl radical.
• polyethersiloxanes of the formula (5) that were hydrosilylated with inclusion of olefins are used, as a result of which R 1 consists to an extent of not less than 10 mol %, preferably to an extent of not less than 20 mol % and more preferably to an extent of not less than 40 mol % of CH 2 —R 8 where R 8 is a linear or branched hydrocarbon having 9 to 17 carbon atoms.
• polyethersiloxanes of the formula (5) in which the terminal positions (also called the alpha and omega positions) on the siloxane are at least partly functionalized with le moieties are used.
• at least 10 mol %, preferably at least 30 mol % and more preferably at least 50 mol % of the terminal positions are functionalized with R 1 radicals.
• polyethersiloxanes of the formula (5) in which a statistical average of not more than 50%, preferably not more than 45%, more preferably not more than 40%, of the total mean molar mass of the siloxane is accounted for by the cumulative molar mass of all the identical or different R 1 radicals in the siloxane are used.
• inventive polyalkylsiloxanes and polyether-modified siloxanes may also be used as part of compositions with different carrier media.
• useful carrier media include glycols, alkoxylates or oils of synthetic and/or natural origin.
• the total proportion by mass of inventive polyalkylsiloxanes and polyether-modified siloxanes in the finished polyurethane foam is from 0.01% to 10% by weight, preferably from 0.1% to 3% by weight.
• inventive combinations of polyalkylsiloxanes and polyether-modified siloxanes are also referred to hereinafter as “mixture”, irrespective of whether the two components are supplied separately or together to the reaction mixture for production of the rigid PU foam.
• the present invention further provides a composition suitable for production of rigid polyurethane or polyisocyanurate foams, comprising at least one isocyanate component, at least one polyol component, at least one foam stabilizer, at least one urethane and/or isocyanurate catalyst, water and/or blowing agent, and optionally at least one flame retardant and/or further additives, which is characterized in that an inventive mixture of polyalkylsiloxanes and polyether-modified siloxanes is present as foam stabilizer, a process for producing rigid polyurethane or polyisocyanurate foams by reacting this composition, and also the rigid polyurethane or polyisocyanurate foams obtainable thereby.
• the present invention additionally provides for the use of rigid polyurethane or polyisocyanurate foams according to the invention as insulation boards and insulant, and also a cooling apparatus which includes a rigid polyurethane or polyisocyanurate foam according to the invention as insulating material.
• the inventive mixture of polyalkylsiloxanes and polyether-modified siloxanes has the advantage of producing rigid polyurethane or polyisocyanurate foams, which are marked by a good fine-cell content and good insulating properties and at the same time have little by way of foam defects.
• a preferred composition of the invention contains the following constituents:
• the proportion by mass of inventive siloxane mixture i.e. polyalkylsiloxanes and polyether-modified siloxanes) d), based on 100 parts by mass of polyol component a
• the proportion by mass of inventive siloxane mixture is preferably from 0.1 to 10 pphp, more preferably from 0.5 to 5 pphp and especially preferably from 1 to 3 pphp.
• Polyols suitable as polyol component a) for the purposes of the present invention are all organic substances having one or more isocyanate-reactive groups, preferably OH groups, and also formulations thereof.
• Preferred polyols are all polyether polyols and/or polyester polyols and/or hydroxyl-containing aliphatic polycarbonates, especially polyether polycarbonate polyols, and/or polyols of natural origin, known as “natural oil-based polyols” (NOPs) which are customarily used for producing polyurethane systems, especially polyurethane coatings, polyurethane elastomers or foams.
• the polyols usually have a functionality of from 1.8 to 8 and number-average molecular weights in the range from 500 to 15 000.
• the polyols having OH numbers in the range from 10 to 1200 mg KOH/g are usually employed.
• Polyether polyols can be prepared by known methods, for example by anionic polymerization of alkylene oxides in the presence of alkali metal hydroxides, alkali metal alkoxides or amines as catalysts and by addition of at least one starter molecule which preferably contains 2 or 3 reactive hydrogen atoms in bonded form, or by cationic polymerization of alkylene oxides in the presence of Lewis acids, for example antimony pentachloride or boron trifluoride etherate, or by double metal cyanide catalysis.
• Suitable alkylene oxides contain from 2 to 4 carbon atoms in the alkylene moiety.
• Examples are tetrahydrofuran, 1,3-propylene oxide, 1,2-butylene oxide and 2,3-butylene oxide; ethylene oxide and 1,2-propylene oxide are preferably used.
• the alkylene oxides can be used individually, cumulatively, in blocks, in alternation or as mixtures.
• Starter molecules used may especially be compounds having at least 2, preferably 2 to 8, hydroxyl groups, or having at least two primary amino groups in the molecule.
• Starter molecules used may, for example, be water, di-, tri- or tetrahydric alcohols such as ethylene glycol, propane-1,2- and -1,3-diol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, castor oil, etc., higher polyfunctional polyols, especially sugar compounds, for example glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resols, for example oligomeric condensation products of phenol and formaldehyde and Mannich condensates of phenols, formaldehyde and dialkanolamines, and also melamine, or amines such as aniline, EDA, TDA, MDA and PMDA, more preferably TDA and PMDA.
• the choice of the suitable starter molecule is dependent on the respective field of application of the resulting polyether polyol in the production of polyurethane.
• Polyester polyols are based on esters of polybasic aliphatic or aromatic carboxylic acids, preferably having 2 to 12 carbon atoms.
• aliphatic carboxylic acids are succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid and fumaric acid.
• aromatic carboxylic acids are phthalic acid, isophthalic acid, terephthalic acid and the isomeric naphthalenedicarboxylic acids.
• polyester polyols are obtained by condensation of these polybasic carboxylic acids with polyhydric alcohols, preferably of diols or triols having 2 to 12, more preferably having 2 to 6, carbon atoms, preferably trimethylolpropane and glycerol.
• polyester polyols based on aromatic carboxylic acids are used at more than 50 pphp, preferably more than 70 pphp, based on 100 parts by mass of polyol component.
• no polyols based on phenolic resins prepared from novolaks and alkylene oxides and no polyols based on aromatic amine polyols prepared by alkoxylation of aromatic amines are used, which means that, in this preferred embodiment, less than 20 pphp, preferably less than 10 pphp, especially less than 2 pphp and most advantageously no polyols at all based on phenolic resins prepared from novolaks and alkylene oxides and no polyols at all based on aromatic amine polyols prepared by alkoxylation of aromatic amines are used.
• Polyether polycarbonate polyols are polyols containing carbon dioxide in the bonded form of the carbonate. Since carbon dioxide forms as a by-product in large volumes in many processes in the chemical industry, the use of carbon dioxide as comonomer in alkylene oxide polymerizations is of particular interest from a commercial point of view. Partial replacement of alkylene oxides in polyols with carbon dioxide has the potential to distinctly lower the costs for the production of polyols. Moreover, the use of CO2 as comonomer is very advantageous in environmental terms, since this reaction constitutes the conversion of a greenhouse gas to a polymer.
• Suitable alkylene oxides and H-functional starter substances are those also used for preparing carbonate-free polyether polyols, as described above.
• Polyols based on renewable raw materials, natural oil-based polyols (NOPs), for production of polyurethane foams are of increasing interest with regard to the long-term limits in the availability of fossil resources, namely oil, coal and gas, and against the background of rising crude oil prices, and have already been described many times in such applications (WO 2005/033167; US 2006/0293400, WO 2006/094227, WO 2004/096882, US 2002/0103091, WO 2006/116456 and EP 1678232).
• a number of these polyols are now available on the market from various manufacturers (WO2004/020497, US2006/0229375, WO2009/058367).
• the base raw material e.g.
• soya bean oil, palm oil or castor oil and the subsequent workup, polyols having a different profile of properties are the result. It is possible here to distinguish essentially between two groups: a) polyols based on renewable raw materials which are modified such that they can be used to an extent of 100% for production of polyurethanes (WO2004/020497, US2006/0229375); b) polyols based on renewable raw materials which, because of the processing and properties thereof, can replace the petrochemical-based polyol only in a certain proportion (WO2009/058367).
• a further class of usable polyols is that of the so-called filled polyols (polymer polyols).
• polymer polyols contain dispersed solid organic fillers up to a solids content of 40% or more.
• SAN, PUD and PIPA polyols are among useful polyols.
• SAN polyols are highly reactive polyols containing a dispersed copolymer based on styrene-acrylonitrile (SAN).
• PUD polyols are highly reactive polyols containing polyurea, likewise in dispersed form.
• PIPA polyols are highly reactive polyols containing a dispersed polyurethane, for example formed by in situ reaction of an isocyanate with an alkanolamine in a conventional polyol.
• a further class of useful polyols are those which are obtained as prepolymers via reaction of polyol with isocyanate in a molar ratio of preferably 100:1 to 5:1, more preferably 50:1 to 10:1.
• prepolymers are preferably made up in the form of a solution in polymer, and the polyol preferably corresponds to the polyol used for preparing the prepolymers.
• a preferred ratio of isocyanate and polyol, expressed as the index of the formulation, i.e. as stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (e.g. OH groups, NH groups) multiplied by 100, is in the range from 10 to 1000 and preferably in the range from 40 to 600.
• An index of 100 represents a molar reactive group ratio of 1:1.
• the index of the formulation is in the range of 150 to 550, more preferably 200 to 500. This means that a distinct excess of isocyanate groups over isocyanate-reactive groups is present. This results in trimerization reactions of the isocyanates, which thus form isocyanurates.
• foam types are also referred to as polyisocyanurate (PIR) foams and are notable for improved fire characteristics, i.e. poorer burning.
• Isocyanate components b) used are preferably one or more organic polyisocyanates having two or more isocyanate functions.
• Polyol components used are preferably one or more polyols having two or more isocyanate-reactive groups.
• Isocyanates suitable as isocyanate components for the purposes of this invention are all isocyanates containing at least two isocyanate groups. Generally, it is possible to use all aliphatic, cycloaliphatic, arylaliphatic and preferably aromatic polyfunctional isocyanates known per se. Isocyanates are more preferably used in a range of from 60 to 200 mol %, relative to the sum total of isocyanate-consuming components.
• alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene radical, e.g. dodecane 1,12-diisocyanate, 2-ethyltetramethylene 1,4-diisocyanate, 2-methylpentamethylene 1,5-diisocyanate, tetramethylene 1,4-diisocyanate and preferably hexamethylene 1,6-diisocyanate (HMDI), cycloaliphatic diisocyanates such as cyclohexane 1,3- and 1,4-diisocyanate and also any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI for short), hexahydrotolylene 2,4- and 2,6-diisocyanate and also the corresponding isomer mixtures, and preferably aromatic diisocyanates and polyisocyanates,
• the organic diisocyanates and polyisocyanates can be used individually or in the form of mixtures thereof. It is likewise possible to use corresponding “oligomers” of the diisocyanates (IPDI trimer based on isocyanurate, biurets, uretdiones). In addition, the use of prepolymers based on the abovementioned isocyanates is possible.
• isocyanates which have been modified by the incorporation of urethane, uretdione, isocyanurate, allophanate and other groups, called modified isocyanates.
• Particularly suitable organic polyisocyanates which are therefore used with particular preference are various isomers of tolylene diisocyanate (tolylene 2,4- and 2,6-diisocyanate (TDI), in pure form or as isomer mixtures of various composition), diphenylmethane 4,4′-diisocyanate (MDI), “crude MDI” or “polymeric MDI” (contains the 4,4′ isomer and also the 2,4′ and 2,2′ isomers of MDI and products having more than two rings) and also the two-ring product which is referred to as “pure MDI” and is composed predominantly of 2,4′ and 4,4′ isomer mixtures, and prepolymers derived therefrom.
• examples of particularly suitable isocyanates are detailed, for example, in EP 1712578, EP 1161474, WO 00/58383, US 2007/0072951, EP 1678232 and WO 2005/085310, which are hereby fully incorporated by reference.
• Suitable catalysts c) in the context of the present invention are all compounds which are able to accelerate the reaction of isocyanates with OH functions, NH functions or other isocyanate-reactive groups and with isocyanates themselves. It is possible here to make use of the customary catalysts known from the prior art, including, for example, amines (cyclic, acyclic; monoamines, diamines, oligomers having one or more amino groups), ammonium compounds, organometallic compounds and metal salts, preferably those of tin, iron, bismuth and zinc. In particular, it is possible to use mixtures of a plurality of components as catalysts.
• the mixtures of siloxanes according to the invention i.e. polyalkylsiloxanes and polyether-modified siloxanes are used.
• PES polyether-modified siloxanes
• PAS polyalkylsiloxanes
• PES polyether-modified siloxanes
• the total amount of the siloxanes used is such that the proportion by mass based on the finished polyurethane is 0.01% to 10% by weight, preferably 0.1% to 3% by weight.
• blowing agents e are optional, depending on which foaming process is used. It is possible to work with chemical and physical blowing agents. The selection of the blowing agent depends greatly here on the type of system.
• a foam having high or low density is produced.
• foams having densities of 5 kg/m 3 to 900 kg/m 3 can be produced.
• Preferred densities are 8 to 800, more preferably 10 to 600 kg/m 3 , especially 30 to 150 kg/m 3 .
• blowing agents used may be corresponding compounds having appropriate boiling points. It is likewise possible to use chemical blowing agents which react with NCO groups to liberate gases, for example water or formic acid.
• blowing agents include liquefied CO2, nitrogen, air, volatile liquids, for example hydrocarbons having 3, 4 or 5 carbon atoms, preferably cyclopentane, isopentane and n-pentane, hydrofluorocarbons, preferably HFC 245fa, HFC 134a and HFC 365mfc, chlorofluorocarbons, preferably HCFC 141b, hydrofluoroolefins (HFO) or hydrohaloolefins, for example 1234ze, 1234yf, 1233zd(E) or 1336mzz, oxygen compounds such as methyl formate, acetone and dimethoxymethane, or chlorinated hydrocarbons, preferably dichloromethane and 1,2-dichloroethane.
• Suitable water contents for the purposes of this invention depend on whether or not one or more blowing agents are used in addition to the water. In the case of purely water-blown foams, preferred values are typically 1 to 20 pphp; when other blowing agents are used in addition, the preferred use amount is reduced to typically 0.1 to 5 pphp.
• Additives f) used may be any substances which are known from the prior art and are used in the production of polyurethanes, especially polyurethane foams, for example crosslinkers and chain extenders, stabilizers against oxidative degradation (known as antioxidants), flame retardants, surfactants, biocides, cell-refining additives, cell openers, solid fillers, antistatic additives, nucleating agents, thickeners, dyes, pigments, color pastes, fragrances, and emulsifiers, etc.
• the process of the invention for producing PU foams can be conducted by the known methods, for example by manual mixing or preferably by means of foaming machines. If the process is carried out by using foaming machines, it is possible to use high-pressure or low-pressure machines. The process of the invention can be carried out either batchwise or continuously.
• a preferred rigid polyurethane or polyisocyanurate foam formulation in the context of this invention gives a foam density of from 5 to 900 kg/m 3 and has the composition shown in Table 1.
• the invention further provides a rigid PU foam obtainable by the process mentioned.
• the rigid polyurethane foam has a density of 5 to 900 kg/m 3 , preferably 8 to 800, especially preferably 10 to 600 kg/m 3 , more particularly 30 to 150 kg/m 3 .
• Rigid polyurethane foam or rigid PU foam is an established technical term.
• the known and fundamental difference between flexible foam and rigid foam is that flexible foam shows elastic characteristics and hence deformation is reversible.
• rigid foam is permanently deformed.
• rigid polyurethane foam is especially understood to mean a foam to DIN 7726 that has a compressive strength to DIN 53 421/DIN EN ISO 604 of advantageously ⁇ 20 kPa, preferably ⁇ 80 kPa, more preferably >100 kPa, further preferably ⁇ 150 kPa, especially preferably ⁇ 180 kPa.
• the rigid polyurethane foam, according to DIN ISO 4590 advantageously has a closed-cell content of greater than 50%, preferably greater than 80% and more preferably greater than 90%.
• the rigid PU foams according to the invention can be used as or for production of insulation materials, preferably insulation boards, refrigerators, insulating foams, roof liners, packaging foams or spray foams.
• the PU foams of the invention can be used advantageously.
• motor vehicle construction especially for production of motor vehicle inner roof liners, bodywork parts, interior trim, cooled motor vehicles, large containers, transport pallets, packaging laminates, in the furniture industry, for example for furniture parts, doors, linings, in electronics applications.
• Cooling apparatuses of the invention have, as insulation material, a rigid PU foam of the invention (polyurethane or polyisocyanurate foam).
• the invention further provides for the use of the rigid PU foam as insulation material in refrigeration technology, in refrigeration equipment, in the construction sector, automobile sector, shipbuilding sector and/or electronics sector, as insulation panels, as spray foam, as one-component foam.
• the polyether-modified siloxanes (PES) used were the following materials:
• the polyalkylsiloxanes (PAS) used were the following materials conforming to the formula (1), M a D b T c Q d , as defined above. These are summarized in Table 2.
• the polyether-modified siloxane and polysiloxanes were used in a mixture or combination.
• Foams were produced using the following raw materials:
• Foaming was carried out by manual mixing.
• the compounds according to the invention, polyols, flame retardants, catalysts, water, siloxane surfactants according to the invention or not according to the invention, polyalkylsiloxanes according to the invention and blowing agents were weighed into a beaker and mixed with a disc stirrer (diameter 6 cm) at 1000 rpm for 30 seconds.
• the blowing agent quantity which had evaporated during the mixing operation was determined by reweighing and replenished.
• the isocyanate (MDI) was added, and the reaction mixture was stirred with the stirrer described at 3000 rpm for 5 s.
• the mixture was introduced immediately into an aluminium mould of dimensions 50 cm ⁇ 25 cm ⁇ 7 cm which had been heated to 65° C.
• the use amount of foam formulation was such that the amount was sufficient for minimum filling of the mould.
• the foams were demoulded after 10 minutes and then stored at room temperature for 24 hours.
• a cut surface in the foam was used to visually assess the degree of internal defects and the pore structure on a scale from 1 to 10, where 10 represents an ongoing foam and 1 a very significantly defective foam.
• the thermal conductivity coefficient ( ⁇ value in mW/m ⁇ K) was measured on 2.5 cm-thick sheets with a device of the Hesto Lambda Control type, model HLC X206, at an average temperature of 10° C. in accordance with the specifications of standard EN12667:2001.

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